Method of dispersing nanoparticles in different mediums and methods to achieve superior thermoelectric performances in carbon nanotube polymer systems
Provided herein is a method for forming a composite. The method can include mixing a plurality of carbon nanotubes (CNTs) and a plurality of magnetic nanoparticles in a non-polar medium. At least some of the plurality of CNTs form entangled CNTs. The method also includes attaching first ones of the plurality of magnetic nanoparticles to exposed surfaces of the entangled CNTs; disentangling the entangled CNTs to form a plurality of dispersed CNTs; and aligning the plurality of dispersed CNTs. The disentangling of the entangled CNTs to form a plurality of dispersed CNTs includes exposing the plurality of magnetic nanoparticles and the plurality of entangled CNTs to electromagnetic energy.
This application claims priority to PCT Patent Application No. PCT/US2015/064281 filed on Dec. 7, 2015, which claims priority to U.S. Provisional patent application Ser. No. 62/088,310 filed Dec. 5, 2014, the entirety of which is hereby incorporated by reference.
FIELDThis invention relates generally to the field of composites, in particular, carbon-nanotube-reinforced composites and methods of making such composites.
BACKGROUNDNanocomposites
A single carbon nanotube has extraordinary mechanical properties, exhibiting a tensile strength of up to 100 times that of high strength steels and a stiffness that is 5 times larger than steel. Thus, one would intuitively expect that the addition of minute amounts of CNTs to another material (to form a so called ‘nanocomposite’) should result in significant improvements in the mechanical properties. Indeed, mathematical models predict an order-of-magnitude increase in the stiffness of polymers upon adding only 1% by volume of randomly distributed CNTs.
Fiber reinforced polymer composites (FRP) are made from continuous and aligned microfibers that are held together by a polymer matrix. FRPs possess very high in-plane strength and stiffness-to-weight ratio. For instance, carbon fiber reinforced composites are three times stronger than steel at the same weight. However, FRPs lack mechanical performance in the cross-plane direction. FRPs are widely used in many applications including automotive, aerospace, and civil infrastructure industries. Contrary to metallic structures, components made form FRP lack plastic deformation prior to failure and thus experience an abrupt failure. Most importantly, delamination and polymer matrix cracking in composites are usually not predictable, resulting in very conservative designs and frequent inspection of FRP structures. Such problems remain the challenges in the art.
Considering the relatively low price of industrial grade CNTs, which can be used as reinforcement in structures (˜$100 per kilogram), they are theoretically the ideal filler for nanocomposites. In fact, the addition of 1% by weight of randomly distributed CNTs to the matrix of an FRP improves impact resistance, strain to failure and off-axis strength by 21%, 12% and 20%, respectively, compared to conventional epoxy FRP. Further, CNTs are capable of eliminating fatigue limitations of glass fiber reinforced polymers. Importantly, addition of small amounts of CNTs to conventional FRPs significantly improves polymer matrix and delamination crack resistance.
However, nanocomposites suffer some shortcomings. Primarily, groups CNTs 101 may become entangled to form side-by-side assemblies of nanotubes, such as bundles 103, 105, and entangled bundles, such as aggregates, as shown in
Despite the great promise of carbon nanotubes (CNTs) for many engineering applications, scalable methods to effectively disperse nanotubes and control their alignment in a matrix, such as a polymer matrix, have not been realized. These limitations have greatly limited the widespread use of carbon nanotubes, especially for structural applications.
To alleviate this drawback, CNT alignment can be utilized to achieve the desired mechanical properties in preferred directions, while requiring much less nanotube loadings. For example, as shown in
Accordingly, a scalable and economical method to disperse nanoparticles (e.g. carbon nanotubes) and control their alignment in polymeric and other mediums, particularly at an industrial scale, would be welcome in the art.
Thermoelectrics
Meanwhile, the development of thermoelectrics, materials that efficiently convert (waste) heat into pollution free electricity, is an essential energy need for today's society. Thermoelectric energy conversion represents a solid-state technology based on the “Thermoelectric effect”, where a temperature gradient generates an electrical current. Conversely, cooling (refrigeration) can be achieved by applying electrical power across the material. The fundamental difficulty in creating efficient thermoelectric materials is that they must be very good in conducting electricity, but not heat. Only for such materials (electrically-conductive but thermally-insulating) a temperature gradient can be maintained across the material while electrons (or holes) diffuse to generate a current. These two properties, however, go hand in hand. Despite 70 years of research, remarkable enhancements in thermoelectrics have been obtained in the past 20 years via the nontraditional technology of nanostructuring.
In general, creating hierarchical structures that allow electron transfer but suppress phonon transport is a commonly practiced strategy to achieve efficient thermoelectrics. Recently, a new class of thermoelectrics based on organic materials has emerged. Organic materials (i.e., polymeric systems with carbon nanomaterials) benefit from many advantages over their inorganic counterparts. Specifically, organic thermoelectrics provide an opportunity for creating flexible modules and even fabrics that can be used in clothing, wearable electronics (e.g., body powered sensor systems for health), and as shapes that conform to complex objects. Moreover, organic thermoelectrics can be integrated into hybrid modules with organic photovoltaics (OPVs), increasing the efficiency of OPVs by converting solar heat into electricity.
The economics and efficiency of current thermoelectrics are not sufficient for commercial usage, and hence they are only found in niche applications such as body heat-powered watches and heating/cooling of seats in luxury brand cars. Moreover, they suffer from other barriers to widespread acceptance because of their difficulty in manufacturing, toxicity, prohibitive cost, and reliance on rare earth materials. While the first generation of thermoelectric devices is being commercialized, the next generation demands lie in designing cheaper and more efficient materials. To address these challenges, organic materials are a particularly attractive alternative to inorganic thermoelectrics, especially for refrigeration or waste heat recovery up to 200° C., in that they are cheap, safe, abundant, and can be produced using scalable roll-to-roll (R2R) processes. R2R refers to processes for creating electronics over flexible plastic substrates using printing, coating, or other scalable techniques.
CNTs are promising materials for thermoelectrics due to their extraordinary electrical properties, air stability, and mechanical flexibility. A single CNT has a flawless structure comprising hexagonal arrays of sp2 connected carbon atoms and therefore has electrical and thermal conductivities on par with the best electrically and thermally conductive materials, respectively. When added as fillers to polymeric materials, CNTs can readily improve electrical properties of the host polymer, tuning it from insulating to conductive. On the contrary, improvement of thermal conductivity in CNT based composites is very minimal As such, CNT-polymer junctions allow electron transport but scatter phonons. Numerous studies have shown that properly engineered nanoscale structures and interfaces allow for the decoupled control of electrical and thermal conductivities in CNT networks and are therefore critical for realizing high ZT values.
Accordingly, methods for incorporating CNTs for use in thermoelectric would be a welcome addition in the art.
SUMMARYIn an embodiment, there is a method for forming a composite, comprising: mixing a plurality of carbon nanotubes (CNTs) and a plurality of magnetic nanoparticles in a non-polar medium, wherein at least some of the plurality of CNTs form entangled CNTs; attaching first ones of the plurality of magnetic nanoparticles to exposed surfaces of the entangled CNTs; disentangling the entangled CNTs to form a plurality of dispersed CNTs; and aligning the plurality of dispersed CNTs, wherein the disentangling of the entangled CNTs to form a plurality of dispersed CNTs comprises exposing the plurality of magnetic nanoparticles and the plurality of entangled CNTs to electromagnetic energy.
In another embodiment, there is a fiber reinforced polymer composite, comprising: a plurality of composite plies extending in a parallel-plane direction, a plurality of aligned carbon nanotubes (CNTs) extending across an inter-ply interface disposed between adjacent ones of the plurality of composite plies, and a plurality of nanoparticles bonded to surfaces of the plurality of aligned CNTs.
In another embodiment, there is a thermoelectric structure, comprising: a polymer interface layer; a first layer disposed on a first side of the polymer interface layer and comprising a plurality of aligned, wavy carbon nanotubes (CNTs), wherein the CNTs are vertically oriented to a surface of the polymer interface layer; a second layer disposed on a second side of the polymer interface layer and comprising a plurality of aligned, wavy CNTs, wherein the CNTs are vertically oriented to the surface of the polymer interface layer; and wherein at least some of the CNTs of the first layer and some of the plurality of CNTs of the second layer comprise defects.
In another embodiment, there is a method of making a thermoelectric structure, comprising: forming a first array of aligned carbon nanotubes (CNTs) on a first substrate, wherein the CNTs of the first array are vertically oriented to a surface of the first substrate; transferring the first array of aligned CNTs onto a second substrate, wherein the aligned CNTs of the first array are vertically oriented to a surface of the second substrate; removing the first substrate to expose ends of the aligned CNTs in the first array; and forming a first polymer layer on the exposed ends of the aligned CNTs, wherein the CNTs of the first array are vertically oriented to a surface of the first polymer layer.
Some embodiments provide for economically viable and scalable nano-manufacturing methods to disperse CNTs in different mediums and control their alignment.
Some embodiments provide for cheap and efficient solutions electricity generation from heat or cooling.
Advantages of the embodiments will be set forth in part in the description which follows, and in part will be understood from the description, or may be learned by practice of the invention. The advantages will be realized and attained by means of the elements and combinations particularly pointed out in the appended claims.
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention, as claimed.
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description, serve to explain the principles of the invention.
Reference will now be made in detail to the present embodiments, examples of which are illustrated in the accompanying drawings. Wherever possible, the same reference numbers will be used throughout the drawings to refer to the same or like parts.
Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements. Moreover, all ranges disclosed herein are to be understood to encompass any and all sub-ranges subsumed therein. For example, a range of “less than 10” can include any and all sub-ranges between (and including) the minimum value of zero and the maximum value of 10, that is, any and all sub-ranges having a minimum value of equal to or greater than zero and a maximum value of equal to or less than 10, e.g., 1 to 5. In certain cases, the numerical values as stated for the parameter can take on negative values. In this case, the example value of range stated as “less that 10” can assume negative values, e.g. −1, −2, −3, −10, −20, −30, etc.
The following embodiments are described for illustrative purposes only with reference to the Figures. Those of skill in the art will appreciate that the following description is exemplary in nature, and that various modifications to the parameters set forth herein could be made without departing from the scope of the present invention. It is intended that the specification and examples be considered as examples only. The various embodiments are not necessarily mutually exclusive, as some embodiments can be combined with one or more other embodiments to form new embodiments.
I. Method of Dispersing Nanoparticles in Different Mediums
In a method of the present invention illustrated in
A. Carbon Nanotubes
The carbon nanotubes of an embodiment may be provided in the mixture with the nanoparticles. In an example, the carbon nanotubes may be provided in an amount of from greater than about 0 wt % up to about 5 wt %. The carbon nanotubes of the embodiments may be single and/or multi-walled nanotubes of any aspect ratio.
B. Nanoparticles
The nanoparticles may be magnetic nanoparticles. The magnetic nanoparticles may comprise any super-paramagnetic nanoparticles and may comprise iron, nickel, cobalt, their oxides and their alloys.
The nanoparticles may be charged nanoparticles. Charged nanoparticles may comprise magnetic nanoparticles coated with charged polymers. The nanoparticles may be functionalized. For example, the magnetic nanoparticles may be functionalized to contain a functional group that may react with a surface of a carbon nanotube, for example, through covalent or hydrogen bonding. In an example, the magnetic nanoparticles comprise a polymeric coating.
In an embodiment, the nanoparticles may attach to the nanotubes via van der walls forces. While not limited to any particular theory, it is believed that if the nanoparticles attach through van der walls forces to the nanotubes, application of a magnetic field, such as an AC magnetic field, can cause the nanoparticles to move and thereby align the nanotubes, for example, side-by-side. A distance between the aligned nanotubes can, therefore, be controlled by the size of the magnetic nanoparticles or the frequency of the AC magnetic filed used in the embodiments. Accordingly, in an embodiment. Accordingly, in an embodiment, the nanoparticles may be defined by at least one dimension that is smaller than or equal to 100 nm. In an embodiment, the nanoparticles may be included in the matrix in an amount of at least about 0.01 wt % to an amount that provides for the alignment of the nanotubes as described herein.
C. Matrix
The CNTs and nanoparticles may be mixed in a medium, for example, a non-polar medium. In some aspects, the medium may comprise a non-polar polymer or solvent. For example, the medium can be any polymer dissolved in a non-polar solvent or a molten polymer. When the CNTs and nanoparticles are combined in the matrix, the nanoparticles may react to decorate surfaces of CNTs.
In an embodiment, magnetic nanoparticles (e.g., iron oxide) can be synthesized via a co-precipitation method in which iron salts are dissolved in a solution and introduced into a basic environment at elevated temperatures. The magnetic nanoparticles can be then stabilized (coated), for example, with oleic acid, to form a coated magnetic nanoparticle (e.g., iron oxide core-oleic acid coating). The coating of the coated magnetic nanoparticles interacts with carbon nanotubes that are functionalized (carboxylated or hydroxylated) and a ligand exchange occurs. The oleic acid may be replaced with the functional groups on the sidewalls of CNTs. This connects the CNTs to the magnetic nanoparticle core, such as an iron oxide core. The magnetic nanoparticles may be placed in a non-polar solvent. For example, the magnetic nanoparticles may be stabilized in a Kerosene solution. Higher temperatures (˜70C) may promote ligand exchange. Mechanical agitation and microwave energy absorption (by the nanotubes) may also promote ligand exchange and cause more nanoparticles to attach to the nanotubes
D. Electromagnetic Energy
In embodiments, electromagnetic energy may cause the nanoparticles to spin or move quickly, thereby agitating CNTs to which they are attached, which in turn agitates neighboring CNTs leading to a disentangling of entangled CNTs.
In an embodiment the electromagnetic energy is provided at frequencies which interact with the nanoparticles. In an example, the electromagnetic energy comprises microwave energy. While not limited to any particular theory, it is believed that the electromagnetic energy interacts with the magnetic nanoparticles. Accordingly, microwave exposure of the magnetic nanoparticles results in well-dispersed CNTs decorated with magnetic nanoparticles, which can later be aligned in an external magnetic field. Thus, in an embodiment, the matrix material may also be selected so that it is transparent to magnetic fields.
E. External Magnetic Field
External magnetic fields with strength as low as 0.001 Tesla can be applied to align nanotubes. Alternating magnetic fields can be applied to place the nanotubes on which nanoparticles are attached at corresponding distances from one another in a 2D fashion.
In an embodiment, the nanoparticles remain attached to the carbon nanotubes. In some embodiments, however, the nanoparticles may be washed away after the nanotubes are aligned. For example, aligned nanotubes that do not have nanoparticles attached thereto may be used in applications such as for field effect transistors and, therefore, the nanoparticles must be washed away prior to incorporation of such nanotubes in the field effect transistors.
In summary, as shown in the flowchart of
Such methods may be used for forming an FRP having a plurality of aligned CNTs that are aligned in the cross-plane direction. While not limited to any particular theory, it is believed that methods of aligning CNTs for use in an FRP provide for anisotropic strengthening that allows for improved properties in desired (weak) directions in a composite and, therefore, smaller loadings of CNTs are required. In one embodiment, an FRP 400 is shown in
II. Methods to Achieve Superior Thermoelectric Performances in Carbon Nanotube Polymer Systems
As used herein “nano-scale” refers to dimensions equal to or lower than 100 nanometers, while “micro-scale” refers to features that are larger than 100 nanometers and smaller than 100 microns.
Aligned CNTs present an interesting alternative for thermoelectric materials where they possess very high and anisotropic electrical conductivity and a tunable Seebeck coefficient (required for a high thermoelectric efficiency). Their thermal conductivity is, however, too high for a thermoelectric material. Thermal conductivity of single CNTs has been reported to be ˜3000 W/mK or higher at room temperature. CNT-CNT interfaces scatter heat carriers significantly. For example, one, two, and three-dimensional CNT networks can have thermal conductivities of approximately 250, 50, and 3 W/mK, respectively. The reduced trend in thermal conductivities is due to the increased point contacts between individual CNTs in higher dimensional networks leading to increased interfacial thermal (also called Kapitza) resistance. Similarly, reduction in the thermal conductivity of individual tubes can be achieved by introducing defects, such as isotopes, vacancies, dopants, etc., in their structures. Accordingly, it has been discovered that high thermal conductivity can be significantly reduced while maintaining a high Seebeck coefficient and electrical conductivity by controlling atomic-, nano-, and micro-scale structures in CNT networks.
Additionally, vertically aligned CNTs offer many advantages over randomly dispersed CNTs and are especially suitable for thermoelectric. For example, 1D CNT assemblies attain a higher electrical conductivity compared to 2D and 3D networks. Also, stable CNT structures can be controlled at the atomic, nano, and micro-scales. For example, at the atomic-scale, chemical or physical methods can introduce modifications to CNT surfaces; at the nano-scale, CNT size, packing density and CNT-CNT contact points which can be used to tune electrical and thermal properties of CNT arrays may be controlled via adjusting synthesis parameters; and at the micro-scale, CNT length can be readily adjusted by changing the synthesis duration. Furthermore, stable CNT structures allow for doping and introducing defects. On one hand, defects can contribute to a reduced thermal conductivity while doping achieves both n- and p-type electrical characteristics required for thermoelectric modules.
The methods of the present invention reduce the thermal conductivity of aligned CNTs by introducing very small amount of defects and waviness along their length. The present embodiments also provide for a multilayer hierarchical CNT-polymer structure which is formed via independent variation of structures at atomic-, nano-, and micro-scales which provide for increased thermoelectric efficiencies. While not limited to any particular theory, it is believed that defects in small amount reduce the thermal conductivity of CNTs while inducing only minimal effect on their electrical conductivity. While not limited to any particular theory, it is believed that inducing waviness along the length of CNTs in a CNT array control the point contacts between the CNTs and therefore reduce their thermal conductivity. Lastly, engineered CNT-polymer interfaces (as shown in
A. Multi-Layer Thermoelectric Structure
In an embodiment shown in
An objective of the embodiments described herein is to create multilayer CNT-polymer structures, such as structure 600, with structural features that are larger than electron mean free path (which allow electron transfer), but still smaller than phonon mean free path (suppress phonon transport), in order to increase ZT. Moreover, phonon scattering at CNT-polymer and CNT-CNT interfaces as well as defect sites are also employed to further reduce the thermal conductivity. As is known to those of ordinary skill in the art, thermal conductivity of CNTs significantly decreases with increasing CNT diameter and decreasing CNT length. Accordingly, in an embodiment the multilayer structure 600 can include CNTs having different diameters, for example, single-walled and multi-walled CNTs, and CNTs having different lengths. In an embodiment, such as a multi-layer structure, CNTs in one layer may have different lengths and/or different diameters than CNTs of a different layer in the structure. Additionally, the polymer interface layer (thickness and properties) affects all thermoelectric properties. Accordingly, CNT diameter and length, polymer thickness and properties, CNT waviness, and CNT doping may be adjusted, as described below, to tune the thermoelectric properties. Atomic-scale defects may be introduced in CNTs via chemical and physical methods, nanoscale interfaces may be created by controlling CNTs waviness and through controlled polymer infusion at the layer interfaces, and micro-scale structures may be controlled by simply adjusting the length of grown CNT layers.
Accordingly, the CNTs 613 in the structure 600 may be straight and/or wavy CNTs. That is, the CNTs may be substantially linear or may have at least one curved portion between ends thereof. The CNTs may comprise various degrees of waviness (i.e., low, medium and high waviness).The CNTs 613 may have lengths in the range of from about 100 μm to about a few millimeters.
Also, the polymer of the interface layer 630 may be selected from any conjugated polymer family including poly(thiophine)s, poly(pyrrole)s, poly(acetylene)s, poly(p-pheneylenevinylene), e.g., poly(3,4-ethylenedioxythiophene):poly(stryrenesulfonate) (PEDOT: PSS), P3HT [Poly(3-hexylthiophene-2,5-diyl)], polyanilines (PANI). PEDOT:PSS in particular may be selected for the interface layers because it readily interacts with CNTs through π-π stacking, and wraps around the CNTs Also, PEDOT:PSS possesses a favorable low intrinsic thermal conductivity (0.1-0.3 W/mK), and a moderately high and tunable electrical conductivity (values between 2-500 S/cm are readily achieved by adding some high boiling solvent to the pre-deposition solution of this polymer). Dimethyl sulfoxide (DMSO) may be added to the precast solution of PEDOT:PSS to achieve different electrical properties for the interface layer (0, 3, and 5% DMSO can be added to achieve low, medium and very high conductivities). The thickness of the polymer-interface layer 630 may be changed by varying the spin-coating speed or alternatively by spray coating processes. In an embodiment, the polymer interface layer 630 may have a thickness of 200 nm or may have a thickness of just a few nanometers. Accordingly, the polymer interface layer 630 may have a thickness of at least 2 nm, for example, from about 2 nm to about 200 nm, such as from about 10 to about 200 nm.
B. Method of Making Multi-layer Thermoelectric Structure
The CNTs of the embodiments can be grown by any suitable synthesis methods that enable growing vertically aligned CNTs, such as those that are anchored to a substrate. CNTs of the embodiments may be synthesized or they may be purchased (for example, NANOPRO™ available from General Nano, LLC of Cincinnati, Ohio). Catalytic chemical vapor deposition (CCVD) is the most readily scalable and least expensive route to grow VACNTs and has been shown to effectively grow high quality CNTs of various diameters and lengths using different catalysts and over different substrates.
In a CCVD of the embodiments as shown in
In an example, intrinsic silicon wafers may be selected as the substrate 705 since they are inexpensive, flat, and suitable for CNT growth. Initially a 20 nm thermal oxide may be grown on the wafers to esoterically insulate the substrate from the Polymer-CNT thermoelectric materials later to be fabricated. A few nanometers-thick catalyst (iron or nickel) layer may be deposited onto the substrate by physical vapor sputtering. Heat treatment of this thin film over the silicon substrate may result in forming nano-islands, which may later serve as the catalyst for CNT growth. The size of the catalyst particles determines the size of the resulting CNTs, and the sizes may be adjusted by changing the initial thickness of the deposited catalyst layer. CNT arrays may be grown on ultra-thin silicon wafers (20 to 125 micron thick) with different lengths, waviness, and diameter. Such CCVD grown CNTs have a catalyst particle attached to their tip. This particle is removed by simple acid treatment or plasma etching if needed.
Length of the CNTs of the embodiment may be controlled by synthesis duration and flow rates of the gases 701. CNT Waviness and CNT diameter may be controlled through catalyst size, growth temperatures and flow rates flow rates of the gases 701. Lastly, defects may be introduced by either plasma treatment or by doping with molecular dopants such as Tetracyanoquinodimethane (TCNQ) and Tetraphenylporphyrin (TPP). In an example, plasma treatment may include introducing a low power O2 plasma to induce atomic scale defects in the carbon nanotubes. However, one benefit of using molecular dopants to introduce the defects lies in their ability to readily change the Seebeck coefficient of CNTs. For example, TCNQ and tpp achieve p- and n-type doping for CNTs, respectively. However, depending on the amount of dopant, thermal conductivity of CNTs may be adversely increased. After fabrication of the vertically aligned CNT network, the polymer may be spray coated (or spin coated) on wafers to attain a thin film polymer-CNT structure.
Multilayer CNT-polymer structures may be fabricated according to a method described in the flow charts 800, 800′ of
The methods of
Next, the Si substrate 905 is fully etched and removed in XeF2 gas as shown in
In a similar fashion, other layers of CNTs and polymers may stacked on top of one another to construct a multilayered thermoelectric material in which all the CNTs feature desirable alignment, density, periodicity, length and waviness. For example, as shown in
Upon removal of silicon, thermal annealing may implemented to ensure the diffusion of CNTs in the polymer layers and adhesion between the different layers. Accordingly, structure 900 with a plurality of layers (depending on the thicknesses of CNT and polymer players) may be fabricated.
In an embodiment, multilayer CNT-polymer structures may be fabricated according to a method described in the flow charts 800, 800′ of
While the invention has been illustrated respect to one or more implementations, alterations and/or modifications can be made to the illustrated examples without departing from the spirit and scope of the appended claims. In addition, while a particular feature of the invention may have been disclosed with respect to only one of several implementations, such feature may be combined with one or more other features of the other implementations as may be desired and advantageous for any given or particular function.
Furthermore, to the extent that the terms “including”, “includes”, “having”, “has”, “with”, or variants thereof are used in either the detailed description and the claims, such terms are intended to be inclusive in a manner similar to the term “comprising.” As used herein, the phrase “one or more of”, for example, A, B, and C means any of the following: either A, B, or C alone; or combinations of two, such as A and B, B and C, and A and C; or combinations of three A, B and C.
Other embodiments of the invention will be apparent to those skilled in the art from consideration of the specification and practice of the invention disclosed herein. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the invention being indicated by the following claims.
Claims
1. A fiber reinforced polymer composite, comprising:
- a plurality of composite plies extending in a parallel-plane direction, wherein each composite ply comprises a plurality of continuous microfibers aligned in the parallel-plane direction,
- a plurality of aligned carbon nanotubes (CNTs) extending across an inter-ply interface disposed between adjacent ones of the plurality of composite plies, wherein each of the aligned carbon nanotubes extends into the composite ply on each side of the inter-ply interface, and
- a plurality of magnetic nanoparticles bonded to surfaces of the plurality of aligned CNTs, wherein the plurality of magnetic nanoparticles comprise a coating comprising a charged polymer.
2. The fiber reinforced polymer composite of claim 1, wherein the plurality of aligned carbon nanotubes comprise up to about 5% by weight of the fiber reinforced polymer composite.
3. The fiber reinforced polymer composite of claim 1, wherein the plurality of aligned carbon nanotubes comprise single walled carbon nanotubes, multi-walled carbon nanotubes, or a combination thereof.
4. The fiber reinforced polymer composite of claim 1, wherein the magnetic nanoparticles comprise iron, nickel, or cobalt.
5. The fiber reinforced polymer composite of claim 1, wherein the magnetic nanoparticles comprise iron oxide.
6. The fiber reinforced polymer composite of claim 1, wherein the magnetic nanoparticles comprise a functional group that reacts with surfaces of the plurality of aligned carbon nanotubes.
7. The fiber reinforced polymer composite of claim 1, wherein the plurality of magnetic nanoparticles are bonded to surfaces of the plurality of aligned CNTs by van der walls forces.
8. The fiber reinforced polymer composite of claim 1, wherein magnetic nanoparticles comprise an amount of at least about 0.01 wt % of the fiber reinforced polymer composite.
9. The fiber reinforced polymer composite of claim 1, wherein the fiber reinforced polymer composite comprises an improved cross-plane electrical conductivity compared to a fiber reinforced polymer composite without the plurality of aligned carbon nanotubes extending across the inter-ply interface disposed between adjacent ones of the plurality of composite plies.
10. The fiber reinforced polymer composite of claim 1, wherein the fiber reinforced polymer composite comprises an improved delamination resistance compared to a fiber reinforced polymer composite without the plurality of aligned carbon nanotubes extending across the inter-ply interface disposed between adjacent ones of the plurality of composite plies.
11. A fiber reinforced polymer composite, comprising:
- a plurality of composite plies extending in a parallel-plane direction, wherein each composite ply comprises a plurality of continuous microfibers aligned in the parallel-plane direction,
- a plurality of aligned carbon nanotubes (CNTs) extending across an inter-ply interface disposed between adjacent ones of the plurality of composite plies, wherein each of the aligned carbon nanotubes extends into the composite ply on each side of the inter-ply interface, and
- a plurality of magnetic nanoparticles bonded to surfaces of the plurality of aligned CNTs, wherein the plurality of magnetic nanoparticles comprise a functional group that reacts with surfaces of the plurality of aligned carbon nanotubes.
12. The fiber reinforced polymer composite of claim 11, wherein the plurality of aligned carbon nanotubes comprise up to about 5% by weight of the fiber reinforced polymer composite.
13. The fiber reinforced polymer composite of claim 11, wherein the plurality of aligned carbon nanotubes comprise single walled carbon nanotubes, multi-walled carbon nanotubes, or a combination thereof.
14. The fiber reinforced polymer composite of claim 11, wherein the magnetic nanoparticles comprise iron, nickel, or cobalt.
15. The fiber reinforced polymer composite of claim 11, wherein the magnetic nanoparticles comprise iron oxide.
16. The fiber reinforced polymer composite of claim 11, wherein the plurality of magnetic nanoparticles comprise a coating comprising a charged polymer.
17. The fiber reinforced polymer composite of claim 11, wherein the plurality of magnetic nanoparticles are bonded to surfaces of the plurality of aligned CNTs by van der walls forces.
18. The fiber reinforced polymer composite of claim 11, wherein magnetic nanoparticles comprise an amount of at least about 0.01 wt % of the fiber reinforced polymer composite.
19. The fiber reinforced polymer composite of claim 11, wherein the fiber reinforced polymer composite comprises an improved cross-plane electrical conductivity compared to a fiber reinforced polymer composite without the plurality of aligned carbon nanotubes extending across the inter-ply interface disposed between adjacent ones of the plurality of composite plies.
20. The fiber reinforced polymer composite of claim 11, wherein the fiber reinforced polymer composite comprises an improved delamination resistance compared to a fiber reinforced polymer composite without the plurality of aligned carbon nanotubes extending across the inter-ply interface disposed between adjacent ones of the plurality of composite plies.
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Type: Grant
Filed: Dec 7, 2015
Date of Patent: Apr 13, 2021
Patent Publication Number: 20180331270
Inventor: Mehran Tehrani (Albuquerque, NM)
Primary Examiner: Jayne L Mershon
Application Number: 15/527,699
International Classification: H01L 35/24 (20060101); H01L 35/34 (20060101); C08J 3/21 (20060101); C08J 7/04 (20200101); C08K 3/04 (20060101); C08K 3/08 (20060101); C08K 3/22 (20060101); B82Y 30/00 (20110101); B82Y 40/00 (20110101);
